DE1493062B2 - Process for alkylating aromatic compounds with olefins - Google Patents
Process for alkylating aromatic compounds with olefinsInfo
- Publication number
- DE1493062B2 DE1493062B2 DE1493062A DE1493062A DE1493062B2 DE 1493062 B2 DE1493062 B2 DE 1493062B2 DE 1493062 A DE1493062 A DE 1493062A DE 1493062 A DE1493062 A DE 1493062A DE 1493062 B2 DE1493062 B2 DE 1493062B2
- Authority
- DE
- Germany
- Prior art keywords
- catalyst
- hydrogen
- olefins
- catalysts
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/48—Silver or gold
- C07C2523/50—Silver
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
300° C und einem Druck von 20,4 atm in Gegenwart von Wasserstoff durchgeführt. Das Molverhältnis von Wasserstoff zu Benzol zu Äthylen beträgt 72: 6:1. Der Katalysator 1 wird durch Behandlung eines Siliciumdioxid - Aluminiumoxid - Crackkatalysators, der 25 Gewichtsprozent Aluminiumoxid enthält, mit einer ammoniakalischen Silbernitratlösung und anschließendem Waschen, Trocknen und Calcinieren hergestellt. Die Katalysatoren 2 und 3 enthalten Silber, Fluor und Siliciumdioxid-Aluminiumoxid und werden hergestellt, indem man das Siliciumdioxid-Aluminiumoxid-Xerogel des Katalysators 1 mit einer wäßrigen Lösung von Ammoniumfluorid, Silbernitrat und Ammoniumhydroxid behandelt. Die Produkte werden dann gewaschen, getrocknet und calciniert. Beim Katalysator 4 ist Silber in H-Mordenit eingebaut, er wird durch Ionenaustausch zwischen einer Silbernitratlösung und der Ammoniumverbindung des Mordenits, nachfolgendem Waschen, Trocknen und Calcinieren hergestellt. Der Vergleichskatalysator 5 enthält Nickel, Fluor und Siliciumdioxid-Aluminiumoxid und wird hergestellt, indem man dem Siliciumdioxid-Aluminiumoxid durch Ionenaustausch Nickelkationen einverleibt. Das Fluorid wird dem Siliciumdioxid-Aluminiumoxid-Hydrogel durch Kontaktieren mit einer Ammoniumfluorid-Lösung einverleibt. Der Katalysator wird vor der Verwendung mit H2S sulfidiert. Der Vergleichskatalysator 6 besteht aus dem Siliciumdioxid-Aluminiumoxid des Katalysators 1.300 ° C and a pressure of 20.4 atm in the presence of hydrogen. The molar ratio of hydrogen to benzene to ethylene is 72: 6: 1. The catalyst 1 is prepared by treating a silica-alumina cracking catalyst containing 25 percent by weight of alumina with an ammoniacal silver nitrate solution, followed by washing, drying and calcining. Catalysts 2 and 3 contain silver, fluorine and silica-alumina and are prepared by treating the silica-alumina xerogel of Catalyst 1 with an aqueous solution of ammonium fluoride, silver nitrate and ammonium hydroxide. The products are then washed, dried and calcined. In the case of catalyst 4, silver is built into H-mordenite; it is produced by ion exchange between a silver nitrate solution and the ammonium compound of the mordenite, followed by washing, drying and calcining. The comparative catalyst 5 contains nickel, fluorine and silica-alumina and is prepared by ion-exchanging nickel cations into the silica-alumina. The fluoride is incorporated into the silica-alumina hydrogel by contacting it with an ammonium fluoride solution. The catalyst is sulfided with H 2 S before use. The comparative catalyst 6 consists of the silica-alumina of the catalyst 1.
ίο Der Vergleichskatalysator 7 wird hergestellt, indem
man das Siliciumdioxid-Aluminiumoxid des Katalysators 1 mit Ammoniumfluorid kontaktiert, anschließend
wäscht, trocknet und calciniert. Der Vergleichskatalysator 8 besteht aus. der Wasserstoffverbindung
des Mordenits, einem synthetischen, kristallinen Aluminiumsilikat. Vergleichskatalysator 9 ist ein handelsüblicher
Alkylierungskatalysator und besteht aus Phosphorsäure auf Kieselgur als Trägermaterial.
Die erhaltenen Ergebnisse sind in der nachstehenden Tabelle I zusammengefaßt.The comparative catalyst 7 is produced by contacting the silicon dioxide-aluminum oxide of the catalyst 1 with ammonium fluoride, then washing, drying and calcining. The comparative catalytic converter 8 consists of. the hydrogen compound of mordenite, a synthetic, crystalline aluminum silicate. Comparative catalyst 9 is a commercially available alkylation catalyst and consists of phosphoric acid on kieselguhr as the carrier material.
The results obtained are summarized in Table I below.
Tabelle I Alkylierung von Benzol mit Äthylen in Gegenwart von WasserstoffTable I Alkylation of benzene with ethylene in the presence of hydrogen
Temperatur = 3000C; Druck = 20,4 atm.Temperature = 300 0 C; Pressure = 20.4 atm.
Molarverhältnisse von Wasserstoff zu Benzol zu Äthylen = 72: 6:1.Molar ratio of hydrogen to benzene to ethylene = 72: 6: 1.
benzolenOEthyl-
benzenesO
a) Menge des Äthylens, die pro Stunde über eine Gewichtseinheit des Katalysators geleitet wird. a ) Amount of ethylene which is passed over a unit weight of the catalyst per hour.
b) Einschließlich Mono-, Di- und Triäthylbenzole. b ) Including mono-, di- and triethylbenzenes.
c) Sulfidiert mit H2S. c ) Sulphided with H 2 S.
Die Tabelle zeigt, daß die Umwandlung mit dem Siliciumdioxid-Aluminiumoxid-Crackkatalysator und dem H-Mordenit sehr niedrig ist.The table shows that the conversion with the silica-alumina cracking catalyst and the H-mordenite is very low.
Die Einverleibung von Fluor in das Siliciumdioxid-Aluminiumoxid hat keine Wirkung auf die Äthylenumwandlung und nur geringe Bedeutung für die Selektivität der Äthylbenzolbildung. Der Zusatz von Silber zu dem Siliciumdioxid-Aluminiumoxid und dem H-Mordenit verbessert die Umwandlung und die Selektivität merkbar. Die Kombination von Silber und Fluor mit Siliciumdioxid-Aluminiumoxid ergibt eine ausgezeichnete Umwandlung und Selektivität. Im Gegensatz dazu weist der sulfidierte Nickel-Fluorid-Siliciumdioxid-Aluminiumoxid-Katalysator wegen der Hydrierung von Äthylen zu Äthan nur eine sehr geringe Selektivität auf. Es ist festzustellen, daß der übliche Phosphorsäure-Alkylierungskatalysator auch bei sehr niedrigen Raumgeschwindigkeiten nur eine sehr niedrige Umwandlung und Selektivität ergibt.The incorporation of fluorine into the silica-alumina has no effect on ethylene conversion and only minor importance for the selectivity of ethylbenzene formation. The addition of silver to the silica-alumina and the H-mordenite improves the conversion and selectivity noticeable. The combination of silver and fluorine with silica-alumina makes one excellent conversion and selectivity. In contrast, the sulfided nickel-fluoride-silica-alumina catalyst because of the hydrogenation of ethylene to ethane, only a very low selectivity. It should be noted that the usual phosphoric acid alkylation catalyst even at very low space velocities only one gives very low conversion and selectivity.
Vergleichsbeispiele 10 bis 12Comparative Examples 10 to 12
In den folgenden Versuchen wird die Wirkung von Wasserstoff auf die Umwandlung bei der Alkylierung von Benzol mit Äthylen gezeigt. Es wird, wie in den vorhergehenden Beispielen, eine Temperatur von 300° C und ein Druck von 20,4 atm verwendet. Jedoch ist in diesem Fall statt Wasserstoff Stickstoff anwesend. Das Molverhältnis von Stickstoff zu Benzol zu Äthylen beträgt 72: 6:1. Die Ergebnisse sind in Tabelle II angegeben. Man sieht, daß mit Siliciumdioxid-Aluminiumoxid als Katalysator überhaupt keine Äthylenumwandlung stattfindet und daß der Silber - Fluorid - Siliciumdioxid - Aluminiumoxid - Katalysator noch besser ist als der Phosphorsäure-Alkylierungskatalysator, obwohl seine Aktivität merklich geringer ist als in den Beispielen 2 und 3.The following experiments examine the effect of hydrogen on conversion in the alkylation of benzene with ethylene. As in the previous examples, a temperature of 300 ° C and a pressure of 20.4 atm was used. In this case, however, nitrogen is present instead of hydrogen. The molar ratio of nitrogen to benzene to ethylene is 72: 6: 1. The results are in Table II given. It can be seen that with silica-alumina as a catalyst, no ethylene conversion takes place at all and that the silver - fluoride - silica - alumina catalyst is even better than the phosphoric acid alkylation catalyst, although its activity is markedly lower is than in Examples 2 and 3.
5 65 6
Tabelle II Alkylierung von Benzol mit Äthylen in Gegenwart von StickstoffTable II Alkylation of benzene with ethylene in the presence of nitrogen
Temperatur = 300° C; Druck = 20,4 atm.Temperature = 300 ° C; Pressure = 20.4 atm.
Molverhältnis von Stickstoff zu Benzol zu Äthylen = 72: 6:1.Molar ratio of nitrogen to benzene to ethylene = 72: 6: 1.
Katalysatorcatalyst
Äthylenumwandlung Ethylene conversion
o/O/
/o/O
% Selektivität zu% Selectivity to
Äthylbenzolen Ethylbenzenes
ÄthanEthane
AG/F/Siliciumdioxid-Aluminiumoxid Siliciumdioxid-Aluminiumoxid H3PO4/KieselgurAG / F / silica-alumina silica-alumina H 3 PO 4 / kieselguhr
3 0 1,23 0 1.2
100 100100 100
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US377484A US3316317A (en) | 1964-06-24 | 1964-06-24 | Alkylation process |
Publications (3)
Publication Number | Publication Date |
---|---|
DE1493062A1 DE1493062A1 (en) | 1968-12-19 |
DE1493062B2 true DE1493062B2 (en) | 1974-02-07 |
DE1493062C3 DE1493062C3 (en) | 1974-09-12 |
Family
ID=23489293
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE1493062A Expired DE1493062C3 (en) | 1964-06-24 | 1965-06-22 | Process for alkylating aromatic compounds with olefins |
Country Status (5)
Country | Link |
---|---|
US (1) | US3316317A (en) |
BE (1) | BE665750A (en) |
DE (1) | DE1493062C3 (en) |
GB (1) | GB1092206A (en) |
NL (1) | NL6507969A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2346308A1 (en) * | 1976-03-30 | 1977-10-28 | Inst Francais Du Petrole | PROCESS FOR ALKYLATION-TRANSALKYLATION OF AROMATIC HYDROCARBONS BY METHANOL |
US4721825A (en) * | 1983-06-17 | 1988-01-26 | Idemitsu Kosan Company Limited | Process for the production of xylene |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA450341A (en) * | 1948-08-03 | N. Ipatieff Vladimir | Process for the catalytic treatment of aromatic compounds | |
US3104268A (en) * | 1962-03-19 | 1963-09-17 | Sinclair Research Inc | Alkylation of aromatics with a zinc oxide, chromium oxide, copper oxide, silica-alumina catalyst |
-
1964
- 1964-06-24 US US377484A patent/US3316317A/en not_active Expired - Lifetime
-
1965
- 1965-06-10 GB GB26347/65A patent/GB1092206A/en not_active Expired
- 1965-06-22 DE DE1493062A patent/DE1493062C3/en not_active Expired
- 1965-06-22 NL NL6507969A patent/NL6507969A/xx unknown
- 1965-06-22 BE BE665750D patent/BE665750A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
DE1493062C3 (en) | 1974-09-12 |
NL6507969A (en) | 1965-12-27 |
BE665750A (en) | 1965-12-22 |
US3316317A (en) | 1967-04-25 |
DE1493062A1 (en) | 1968-12-19 |
GB1092206A (en) | 1967-11-22 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
C3 | Grant after two publication steps (3rd publication) | ||
E77 | Valid patent as to the heymanns-index 1977 | ||
EHJ | Ceased/non-payment of the annual fee |